Behaviour of lithium and its isotopes during weathering in the Mackenzie Basin, Canada

International audienceWe report Li isotopic compositions, for river waters and suspended sediments, of about 40 rivers sampled within the Mackenzie River Basin in northwestern Canada. The aim of this study is to characterize the behaviour of Li and its isotopes during weathering at the scale of a large mixed lithology basin. The Mackenzie River waters display systematically heavier Li isotopic compositions relative to source rocks and suspended sediments. The range in delta Li-7 is larger in dissolved load (from +9.3 parts per thousand to +29.0 parts per thousand) compared to suspended sediments (from 1.7 parts per thousand to +3.2 parts per thousand), which are not significantly different from delta Li-7 values in bedrocks. Our study shows that dissolved Li is essentially derived from the weathering of silicates and that its isotopic composition in the dissolved load is inversely correlated with its relative mobility when compared to Na. The highest enrichment of Li-7 in the dissolved load is reported when Li is not or poorly incorporated in secondary phases after its release into solution by mineral dissolution. This counterintuitive observation is interpreted by the mixing of water types derived from two different weathering regimes producing different Li isotopic compositions within the Mackenzie River Basin. The incipient weathering regime characterizing the Rocky Mountains and the Shield areas produces Li-7 enrichment in the fluid phase that is most simply explained by the precipitation of oxyhydroxide phases fractionating Li isotopes. The second weathering regime is found in the lowland area and produces the lower delta Li-7 waters (but still enriched in Li-7 compared to bedrocks) and the most Li-depleted waters (compared to Na). Fractionation factors suggest that the incorporation of Li in clay minerals is the mechanism that explains the isotopic composition of the lowland rivers. The correlation of boron and lithium concentrations found in the dissolved load of the Mackenzie Rivers suggests that precipitation of clay minerals is favoured by the relatively high residence time of water in groundwater. In the Shield and Rocky Mountains, Li isotopes suggest that clay minerals are not forming and that secondary minerals with stronger affinity for Li-7 appear. Although the weathering mechanisms operating in the Mackenzie Basin need to be characterized more precisely, the Li isotope data reported here clearly show the control of Li isotopes by the weathering intensity. The spatial diversity of weathering regimes, resulting from a complex combination of factors such as topography, geology, climate and hydrology explains, in fine, the spatial distribution of Li isotopic ratios in the large drainage basin of the Mackenzie River. There is no simple relationship between Li isotopic composition and chemical denudation fluxes in the Mackenzie River Basi

Lithium isotopes in low and high temperature hydrosystems

International audienceAssessing the origin and behaviour of lithium and the distribution of Li isotopes in hydro-systems is of major importance in order to increase our knowledge of the lithium cycling at the Earth's surface. Lithium is a fluid-mobile element and due to the large relative mass difference between its two stable isotopes, it is subject to significant low and high temperature mass fractionation which provides key information on the nature of water/rock interaction processes. The main objective of the present work is to constrain the behaviour of Li and its isotopes by focusing on three different hydrosystems: rainwaters, river waters and deep geothermal waters

Comparison of dissolved inorganic and organic carbon yields and fluxes in the watersheds of tropical volcanic islands, examples from Guadeloupe (French West Indies)

International audienceOrganic matter is an important factor that cannot be neglected when considering global carbon cycle. New data including organic matter geochemistry at the small watershed scale are needed to elaborate more constrained carbon cycle and climatic models. The objectives are to estimate the DOC and DIC fluxes exported from small tropical watersheds and to give strong constraints on the carbon hydrodynamic of these systems. To answer these questions, we have studied the geochemistry of eleven small watersheds around Basse-Terre volcanic Island in the French West Indies during different hydrological regimes from 2006 to 2008 (i.e. low water level versus floods). We propose a complete set of carbon measurements, including DOC and DIC concentrations, δ13C data, and less commonly, some spectroscopic indicators of the nature of the organic matter. The DOC/DIC ratio varies between 0.07 and 0.30 in low water level and between 0.25 and 1.97 during floods, indicating that organic matter is mainly exported during flood events. On the light of the isotopic composition of DOC, ranging from -32.8 to -26.2 ‰ during low water level and from -30.1 to -27.2 ‰ during floods, we demonstrate that export of organic carbon is mainly controlled by perennial saprolite groundwaters, except for flood events during which rivers are also strongly influenced by soil erosion. The mean annual yields ranged from 2.5 to 5.7 t km-2 yr-1 for the DOC and from 4.8 to 19.6 t km-2 yr-1 for the DIC and exhibit a non-linear relationship with slopes of watersheds. The flash floods explain around 60% of the annual DOC flux and between 25 and 45% of the DIC flux, highlighting the important role of these extreme meteorological events on global carbon export in small tropical volcanic islands. From a carbon mass balance point of view the exports of dissolved carbon from small volcanic islands are important and should be included in global organic carbon budgets

Controls on the Mg Cycle in the Tropics: Insights from a Case Study at the Luquillo Critical Zone Observatory

AbstractTo better constrain the mechanisms controlling short-term Mg dynamics in the tropics, we sampled critical zone compartments of a catchment covered by thick, highly weathered regolith. Our Mg and δ26Mg data indicate that rain is a main source of Mg throughout the regolith, and we do not observe Mg isotope offsets in vegetation/surficial pore water. In addition to rain and weathering inputs, a heavy isotope excursion at ∼1 m depth indicates a fractionation process, likely sorption-desorption or clay dissolution. Stream water δ26Mg reflects inputs from rain and a heavy source, likely differential weathering along deep bedrock fractures

Human-triggered magnification of erosion rates in European Alps since the Bronze Age

A major feature of the Anthropocene is the drastic increase in global soil erosion. Soil erosion is threatening Earth habitability not only as soils are an essential component of the Earth system but also because societies depend on soils. However, proper quantification of the impact of human activities on erosion over thousands of years is still lacking. This is particularly crucial in mountainous areas, where the highest erosion rates are recorded. Here we use the Lake Bourget catchment, one of the largest in the European Alps, to estimate quantitatively the impact of human activities on erosion. Based on a multi-proxy, source-to-sink approach relying on isotopic geochemistry, we discriminate the effects of climate fluctuations from those of human activities on erosion over the last 10,000 years. We demonstrate that until 3800 years ago, climate is the only driver of erosion. From that time on, climate alone cannot explain the measured rates of erosion. Thanks to an unprecedented regional paleoenvironmental reconstruction, we highlight that the development of pastoralism at high altitudes from the Bronze Age onwards and the extension of agriculture starting in the Middle Ages were key factors in the drastic increase in erosion observed in the Alps

Evolution of the alpine Critical Zone since the Last Glacial Period using Li isotopes from lake sediments

Comprehending and predicting the way humans affect the Earth's Critical Zone remains a challenge. An understanding of the past changes resulting from human and non-human influences in the dynamics of the Critical Zone is crucial. Here, we use a retrospective approach to address this question based on a new lithium (Li) isotope record from the Late Glacial Period to the present from a pre-Alpine lake sediment sequence (Lake La Thuile, France). Coupled with the lake sediment archive, the investigation of present-day soils in the lake catchment suggests that lake sediments are not necessarily recording the erosoin of topsoil in the catchment. Our findings indicate that soil particles can be sorted during transportation to the lake, with finer particles being preferentially mobilized, highlighting the influence of fine particle transport on the Li isotope signature of soils and lake sediments. Characterized by low Li isotope signatures, changes in weathering signatures in lake sediments can be amplified by the combined effect of soil development and selective transport. In the La Thuile catchment, soil development was limited during the Late Glacial Period, whereas it became a dominant process during the Holocene climatic optimum together with enhanced selective transport of fine particles. Human activities since 3,000–4,000 yr cal BP induced a strong perturbation hindering both soil formation and selective transport by reinforcing erosion rates. After a period of topsoil destruction caused by intense deforestation and agriculture, lake Li isotopes record the evolution of soil profiles associated with changes in agricultural practices

Predominant floodplain over mountain weathering of Himalayan sediments (Ganga basin)

Author Posting. © The Author(s), 2011. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 84 (2012): 410-432, doi:10.1016/j.gca.2012.02.001.We present an extensive river sediment dataset covering the Ganga basin from the Himalayan front downstream to the Ganga mainstream in Bangladesh. These sediments were mainly collected over several monsoon seasons and include depth profiles of suspended particles in the river water column. Mineral sorting is the first order control on the chemical composition of river sediments. Taking into account this variability we show that sediments become significantly depleted in mobile elements during their transit through the floodplain. By comparing sediments sampled at the Himalayan front with sediments from the Ganga mainstream in Bangladesh it is possible to budget weathering in the floodplain. Assuming a steady state weathering regime in the floodplain, the weathering of Himalayan sediments in the Gangetic floodplain releases ca. (189 ± 92)109 and (69 ± 22)109 moles/yr of carbonate bound Ca and Mg to the dissolved load, respectively. Silicate weathering releases (53 ± 18)109 and (42 ± 13)109 moles/yr of Na and K while the release of silicate Mg and Ca is substantially lower, between ca. 0 and 20109 moles/yr. Additionally, we show that sediment hydration, [H2O+], is a sensitive tracer of silicate weathering that can be used in continental detrital environments, such as the Ganga basin. Both [H2O+] content and the D/H isotopic composition of sediments increases during floodplain transfer in response to mineral hydrolysis and neoformations associated to weathering reactions. By comparing the chemical composition of river sediments across the floodplain with the composition of the eroded Himalayan source rocks, we suggest that the floodplain is the dominant location of silicate weathering for Na, K and [H2O+]. Overall this work emphasizes the role of the Gangetic floodplain in weathering Himalayan sediments. It also demonstrates how detrital sediments can be used as weathering tracers if mineralogical and chemical sorting effects are properly taken into account.This work was supported by INSU program “Relief de la Terre” and ANR Calimero. Valier Galy was supported by the U.S. National Science Fundation (Grant OCE-0851015)

Steering Operational Synergies in Terrestrial Observation Networks: Opportunity for Advancing Earth System Dynamics Modelling

Advancing our understanding of Earth system dynamics (ESD) depends on the development of models and other analytical tools that apply physical, biological, and chemical data. This ambition to increase understanding and develop models of ESD based on site observations was the stimulus for creating the networks of Long-Term Ecological Research (LTER), Critical Zone Observatories (CZOs), and others. We organized a survey, the results of which identified pressing gaps in data availability from these networks, in particular for the future development and evaluation of models that represent ESD processes, and provide insights for improvement in both data collection and model integration. From this survey overview of data applications in the context of LTER and CZO research, we identified three challenges: (1) widen application of terrestrial observation network data in Earth system modelling, (2) develop integrated Earth system models that incorporate process representation and data of multiple disciplines, and (3) identify complementarity in measured variables and spatial extent, and promoting synergies in the existing observational networks. These challenges lead to perspectives and recommendations for an improved dialogue between the observation networks and the ESD modelling community, including co-location of sites in the existing networks and further formalizing these recommendations among these communities. Developing these synergies will enable cross-site and cross-network comparison and synthesis studies, which will help produce insights around organizing principles, classifications, and general rules of coupling processes with environmental conditions

A Rouse-based method to integrate the chemical composition of river sediments : application to the Ganga basin

Author Posting. © American Geophysical Union, 2011. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 116 (2011): F04012, doi:10.1029/2010JF001947.The Ganga River is one of the main conveyors of sediments produced by Himalayan erosion. Determining the flux of elements transported through the system is essential to understand the dynamics of the basin. This is hampered by the chemical heterogeneity of sediments observed both in the water column and under variable hydrodynamic conditions. Using Acoustic Doppler Current Profiler (ADCP) acquisitions with sediment depth profile sampling of the Ganga in Bangladesh we build a simple model to derive the annual flux and grain size distributions of the sediments. The model shows that ca. 390 (±30) Mt of sediments are transported on average each year through the Ganga at Haring Bridge (Bangladesh). Modeled average sediment grain size parameters D50 and D84 are 27 (±4) and 123 (±9) μm, respectively. Grain size parameters are used to infer average chemical compositions of the sediments owing to a strong grain size chemical composition relation. The integrated sediment flux is characterized by low Al/Si and Fe/Si ratios that are close to those inferred for the Himalayan crust. This implies that only limited sequestration occurs in the Gangetic floodplain. The stored sediment flux is estimated to c.a. 10% of the initial Himalayan sediment flux by geochemical mass balance. The associated, globally averaged sedimentation rates in the floodplain are found to be ca. 0.08 mm/yr and yield average Himalayan erosion rate of ca. 0.9 mm/yr. This study stresses the need to carefully address the average composition of river sediments before solving large-scale geochemical budgets.This work was supported by INSU program “Relief de la Terre” and ANR Calimero. Valier Galy was supported by the U.S. National Science Foundation (grant OCE‐0851015)

Sulfur isotopes in rivers : insights into global weathering budgets, pyrite oxidation, and the modern sulfur cycle

This research was funded by a Foster and Coco Stanback postdoctoral fellowship and a Marie Curie Career Integration Grant (CIG14-631752) to AB. JFA acknowledges the support of NSF-OCE grant 1340174 and NSF-EAR grant 1349858. WF acknowledges the support of a grant from the David and Lucile Packard Foundation.The biogeochemical sulfur cycle is intimately linked to the cycles of carbon, iron, and oxygen, and plays an important role in global climate via weathering reactions and aerosols. However, many aspects of the modern budget of the global sulfur cycle are not fully understood. We present new δ34S measurements on sulfate from more than 160 river samples from different geographical and climatic regions—more than 46% of the world's freshwater flux to the ocean is accounted for in this estimate of the global riverine sulfur isotope budget. These measurements include major rivers and their tributaries, as well as time series, and are combined with previously published data to estimate the modern flux-weighted global riverine δ34S as 4.4 ± 4.5‰ (V-CDT), and 4.8 ± 4.9‰ when the most polluted rivers are excluded. The sulfur isotope data, when combined with major anion and cation concentrations, allow us to tease apart the relative contributions of different processes to the modern riverine sulfur budget, resulting in new estimates of the flux of riverine sulfate due to the oxidative weathering of pyrites (1.3 ± 0.2 Tmol S/y) and the weathering of sedimentary sulfate minerals (1.5 ± 0.2 Tmol S/y). These data indicate that previous estimates of the global oxidative weathering of pyrite have been too low by a factor of two. As pyrite oxidation coupled to carbonate weathering can act as a source of CO2 to the atmosphere, this global pyrite weathering budget implies that the global CO2 weathering sink is overestimated. Furthermore, the large range of sulfur isotope ratios in modern rivers indicates that secular changes in the lithologies exposed to weathering through time could play a major role in driving past variations in the δ34S value of seawater.PostprintPostprintPostprintPeer reviewe